Catalyzed reactions between hydrogen sulfide or dimercaptans and dialkenyl ethers orpolyalkenyl amines



Patented Oct. 2 7, 1951i;

GEN isULFIDE on DIMERCAPTANS AND VDIALKENYL ETHERS R POLYALK-ENYL yAMINES William Vaughan, Berkeley, and Denham (Harman, Menlo Park, Calif., assignorsto Shell ADevel'op'ment Co'mpany, San Francisco, Calif., acorpratonof-Delaware No- Drawing. `Application 'Junef22, 1'950, Serial No. 169,772

#reclama (onzen-i583) A"1 'This 'iriventihriates to a 'method Yfor me i ation "bf fnve'l "lubricating `compositions Lbythe base-catalyzed reaction ofliydrog'ensul'- A :tld"e"o`1"`'adiinercalptan:withan olenic compound,

Thisapplioation is a continuationeinpartofapipii'ationse'rial `No.:703,194,'filed November 6,

1946,' andfnovv abandoned. y

-Itis an 4objectief `"the present invention Vto I"provide,'a' novel method for Ythe productionfof a Cii'on-hydrocarbon"lubricant. vIt is another object 'fjthe present-invention to provide a *novel 'liethod for the preparation of 3a llubricant :use-

Y 'ful 'at "lovv temperatures. 'It` is still lanothenobl#taludesoxy-a.s"i7rell asflthioethers) or apolyal- `thelpresence of a-basic'ca'talyst. aotan-tsof v-the i present invention are 'those All-lflavi'n'g the general formula wherein the Rs represent alkenyl radicals (which term Y-is 'e'rnploye'dffherein vto include rboth i substitutel as Well a'sunsub'stituted alkenyl radicals), 'ivl-iilexrepesents:iO-h, -`S-', or

,MR it l 1 "faire, for example, divinyl sulfide, diallylsuldemo 'rior 1-lubricating cornpositionsv y y o yan fy1amins-minnaar@bef Yaisenana-'fe'tipiciyeu inane-tracasfithegmvnuoni aredivinyl amine, '-diallyl amine, dimethallyl amine, -dicrotyl amine, diisopropenyl amine, methyl --diallyl amine, triallyl amine, methyl allyl methallyl amine, dioctyl amine, as Well as substituted polyalkenyl amines,r such as di-(betachlorovinyl) amine, -chloromethyl diallyl amine andthe like. i

A particularly suitable and preferred group of oleiinic reactants -comprises those compounds containing olenic linkages in the alpha and omega positions (i. e., in the terminal positions) of the yrnolecule. Numerous examples of such compounds, including the divinyl, diallyl andfdimethallyl ethers and amines, are given in Vthe lfloregoing paragraph `and need not be repeated ere.

The sulfur-containing reactant of the present inventionis `represented by hydrogen sulde or by adimercaptan. One class of suitable dimercaptan reactants is --made nup of the poli/methylene diniercaptans of the general formula HSfHzM-HSLwherein n is any integer of from 1 to about Y176. In the `majority'of cases, Aitisfpreferable to employ .the normal or isoalkyl chain 'mercaptans having terminal thiov groups, .particularly those which are contained in o'r de- 'riv'e'd 'from "petroleum or petroleum products. Representative di'rnercapt'an'reactants are: 1,2- thanedithiol, 1,2-'propaiiedithioL 1,4-butanedithiol, Vl,ii-'octanedithiol, LIS-hexadeca'nedithiol, l,3dithio142-inethylpropana 1,5-dit'hiol-2-m'et'hyl-3#chloroc'n'entane, "lA-hexanedithiol, and 1,3- pentaned'ithiol.

The V'catalystsemplbyed'in the 'present invention are basic substances which may be 'either "inorganic'orpr'ganic vThe alkali metal oxides, amides, carbonatos v"and h'ydroxi'ds, such as "sodiumfpotassiuin 'and 4'lithium hydroxides, are 'suitable `Illikvvise, "the alkaline earth metal oxides, far'rii'deacarbonates vand l'iydroxides such Vasbariuin calcium, and aluminum hydroxides maybe-used.

Another v'group of catalysts which are useful in theuformation'of; adducts containingnlubricating fractions have the general formula Primary amine catalysts having the general formula H H-ils-R,

include hydroxylamine and alkylamines, espe-A cially alkylamines wherein the alkyl group contains less than thirteen carbon atoms. These include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, ethylenediamine, and their homologs and analogs. Other groups of useful primary amines are the aryl amines, such as phenylamine, and naphthylamine, and substituted aryl amines, including the alkarylam'mes. Examples of such compounds are ortho-toluidine, meta-toluidine, para-toluidine, ortho-sth ylaniline, meta-ethylaniline, and para-ethylaniline. Other primary aromatic amines include ortho phenylenediamine, meta phenylenediamine, para-phenylenediamne as well as substituted phenylenediamines such as methyl-paraphenylenediamine, ethyl para phenylenediamine, etc.

Secondary amines suitable for catalysing the formation of the subject lubricants include dialkylamines containing similar or different alliyl groups, such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, and ethylamylamine, as well as their homologs and analogs. It is preferred, when using dialkylamines as catalysts, that the alkyl substituents be similar alkyl groups, each containing less than about ten carbon atoms. Other secondary amines which act as suitable catalysts include the diarylamines. such as diphenylamine, dinaphthylamine, and phenylnaphthylamine and substituted diarylamines such as 4,4dimethyldiphenylamine, 4,4- dihydroxydiphenylamine, etc. Mixed aromatic aliphatic secondary amines are suitable catalysts. These include amines containing a phenyl substituent and a lower alkyl substituent, for example, such as phenylmethylamine.

Tertiary amines likewise act as catalysts for the preparation of adducts from which the subject lubricants are derived. The outstanding members of this group are triallrylamineasuch as trimethylamine, triethylamne, triisopropylamine, tributylamines, etc. Other suitable catalysts are the quaternary ammonium bases.

A preferred group of basic catalysts for the purpose of the present invention is made up of the aliphatic amines and the alkali metal hydroxides. Y

In thepreparation of the adducts, the ratio of unsaturated compound to the hydrogen suliide or mercaptan may vary within relatively Wide limits, dependent upon the product desired and the other conditions employed. Preferably, the molar ratio of unsaturate to hydrogen sulfide or mercaptan is from 0.5 to about 2.5 and optimum results usually are obtained When the molar ratio is about l.

The molar ratio of catalyst likewise may vary, but it is preferred that the catalyst be present in amounts from about 1 mol percent to about 10 mol percent based on the total mols of unsaturate and hydrogen sulfide or mercaptan, and, under the best conditions for operation, from about 2 to about 5 mol percent is employed.

When operating in an open system, this ratio of catalysts to reactants may be substantially different, since the reactants may, for example, be bubbled in gaseous form through a large excessvv of an amine, which would be either in liquid forni or in solution. Again, if the reaction is conducted entirely in the gaseous phase, the reactants being recycled at a relatively rapid rate through a heated reaction zone, the catalyst concentration may be higher than about l0 mol percent in order to promote maximum formation of the adduct during each cycle.

The reaction may be carried out in a closed system, such as in an autoclave, or the system may be an open one, the reactants being recycled either continuously or batch-wise to the reaction zone.

The adducts are readily formed at a rate convenient for accurate control if the temperature of the reaction zone is from about 70 C. to about 200 C., and usually S30-150 C. is the preferred range.V Lower temperatures may be employed if the concentration of base catalyst and/or the reaction time are increased.

Preferably, the reaction is allowed to continue for 5 to 80 hours, dependent upon the conditions employed. Usually a period of 10 to 50 hours allows the preparation of a product having a large lubricating fraction.

Diluents may be employed during the adduct formation, the diluent being either a gas or liquid, preferably substantially inert to the catalyst or any of the reactants, although maximum reaction rates and lubricant recovery eciency are ordinarily obtained in the absence of diluents. rhe diluent, if used, may act as a solvent for one or more ci the reaction components, as a medium for the adduct formation, as a solvent for the lubricant fraction of the adduct, or as a reuxing agent for the control of reaction temperature.

Although the reaction usually is carried out in a single liquid phase, it may be conducted in an emulsion system or in gaseous phase as well.

An essential feature of the present invention is the substantially complete removal of the volatile components of the adduct. Since the adduct reaction usually results in the formation of a mixture of products, this relatively volatile fraction will vary, dependent upon the conditions under which the add-uct is formed. The catalyst employed will have a great effect upon the proportion of relatively volatile components in the product.

When basic substances are used to catalyze the formation of the adduct, it has been found in accordance with this invention, that the proportion of fractions having lubricating properties is unusually high, as compared with the yield obtained when other catalysts are employed.

The fraction of relatively volatile constituents removed'will depend upon the lubricating purn pose for which the remainder will be employed. 1f no fraction is removed, the composite adduct is generally useless as a lubricant, since the lighter fractions will inevitably volatlize during operation to a greater or lesser degree dependent upon conditions to .which the adduct is subjected.

It has been found that by removing the fraction volatilizing below about C. at 5 om. mercury pressure there is obtained a residue having utility for general lubricating purposes, although to obtain a lubricant having optimum properties it is necessary to remove the fraction volatilizing below about C. at 0.2 cm. mercury pressure.

The lubricant so obtained may be further treated in order: to improve color, alter terminal groups, increase molecular Weight, etc., if desired. The adducts formed by the above reaction may contain sulfhydryl, or mercapto groups' attached to one of the car-bon atoms initially havingl 4an ratom are treated with hydrogen sulfide or a dimercaptan as described hereinbefore, the adducts are polymeric compounds having units of the general configuration,

wherein X is either .J-.S-, Oeor R1 being a hydrogen atom or an alkyl, alkenyl or other monovalent organic radical, and each R is an organic radical, preferably 'a saturated hydrocarbon radical.

The addition reaction of the present invention proceeds in accordance with the Markownikoff rule and therefore results in the formation of compounds having a branched hydrocarbon chain attached directly to the sulfur atom. Thus, when the adduct is one formed between hydrogen sulde and diallyl ether, the principal product of the reaction is a mixture of polymers having units of the general formula:

When an unsaturated thioether or amine is treated with hydrogen sulfide, polymers are produced having a formula which correspond to that above, except that the oxygen atoms are replaced 'by sulfur or nitrogen atoms, as the case may be.

The method of the present invention is parti-cularly usefulin the preparation of lubricants since the use of basic catalysts enables the production of reaction mixtures a large fraction of which possesses lubricating properties. *The adducts making up such lubricant fraction are stable to oxidation and -respond well to treatment with antioxidants such as 1,2-dihydroxybenzene, for example. They have low pour points` (usually lower than 30 F.)l and exhibit exceptionally good extremepressure characteristics.

Eample I Thirty parts hydrogen sulfide, 73.6 parts diallyl ether and parts di-normal-butylamine were heated together at 100 C'. for 89 hours in an autoclave. The viscous, water-white product was then heated at 240 C. under 0.2 cm. mercury pressure in order to remove volatile constituents. The product had the viscosity characteristics of an SAE 70 oil, a viscosity index of 140 and a pour point of 50 F.

The process described in the preceding paragraph was then repeated using 9 parts of diallyl amine instead of the 10 parts of di-n-butylamine as catalyst, the reactants being heated for 45 hours at 100 C. in the bomb. The characteristics of the lubricant fraction so produced were essentially the same as those described above. Likewise, in another operation wherein the amine catalyst is replaced by an equivalent amount of sodium hydroxide, again with a heating period of approximately 45 hours'at 100 C., substantially the same lubricant product is obtained.

(30 parts) and n-butylamine (3.7 parts) were brioant properties.

heated to about 240 C. vat 0.2 cm. mercury pressure to remove Volatile constituents. The viscous i bottoms remaining in the still had a refractive index (n 20/D) of 1.4973 and'manifest'ed good lubricant properties.

Example III Diallyl amine (79 parts) and hydrogen sulfide (30 parts) were heated together at 115 C..for 20 hours in a bomb, the diallyl amine reactant also serving to catalyze the reaction. The some-- what viscous, amber-colored vliquid product Vwas filtered and then topped in a Claisen flask to a kettle temperature of 210 C. at a pressure of .18 cm. mercury. The residue, a dark, amber-colored viscous liquid, was then redistilled to remove still further. volatile constituents, leaving .a -viscous residue boiling above 210 'C. at 0.2 cm. mercury pressure. The latter residue, in addition to having good lubricant qualities, also -forms a useful asphalt-bonding additive.

dimethallyl amine and 28 parts of'hydrogen sulfide. Here again, the residueboiling above 210 Y C. at 0.2 cm. mercury pressure was foundztohave good lubricant qualities.

Example V .s Following the procedure outlined :in `Example I, there is obtained a fraction Vboiling above 200 C. at 0.2 cm. mercury pressure .by ireacting 8555 parts diallyl thioether with .30 parts Vhydrogen' sulfide in the presence of l0 parts Adien-butyl amine. rlihis fraction has a low pour point and makes an excellent lubricant which can be usedA at temperatures well below freezing.

Example VI Following the procedureoutline'in Example I, a liquid having good lubricant qualities atflow temperatures is obtained by` reacting 73.6 parts diallyl ether, 82.7 `parts v1,2-ethanedi-thiol `and 10' parts di-n-butylamine. The non-volatile y.portion of the reaction product, which boilssahom 170 C. at 0.2 cm. mercury pressure, .hasgood lue: A somewhat higher :boiling residue, which also manifests goodlubricant'qual. ities, is obtained by conducting the foregoing reaction With an equivalent amount of 1,16-hexadecanedithiol instead of the 1,2-ethanedithiol.

The invention claimed is:

1. The process which comprises heating diallyl ether and hydrogen sulfide in the presence of from l to 10 mol per cent of di-n-butylamine and removing from the product so formed the fraction thereof volatilizing below about C. at 5 cm. mercury pressure.

2. The process which comprises heating diallyl ether and hydrogen sulde in the presence of 1 to 10 mol per cent of an aliphatic amine and removing from the product so formed the fraction thereof volatilizing belowabout 100 C. at 5 cm. mercury pressure.

3. The process which comprises heating diallyl ether and hydrogen sulde in the presence of 1 to 10 mol per cent of an alkyl amine .bearing an alkyl group having less than 13 carbon atoms and removing from the product so formed the fraction thereof Volatilizing below about 100 C. at 5 om. mercury pressure.

4. The process which comprises heating diallyl 7 ether and hydrogen sulfide in the presence of 1Y to 10 mol per cent of a dialkyl amine, wherein the alkyl radicals each contain less than 10 carbon atoms, and removing from the product so formed the fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure.

5. The process which comprises heating diallyl ether and hydrogen suliide in the presence of from 2 to 5 mol per cent of di-n-butylamine and removing from the product so formed'the fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure.

6. The process which comprises heating dimethallyl ether and hydrogen sulfide in the presence of 1 to 10% of an aliphatic amine and removing from the product so formed the fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure.

7. The process which comprises heating diallyl amine and hydrogen sulfide and removing from the product so formed the fraction thereof Volatilizing below about 100 C. at 5 cm. mercury pressure, the diallyl amine in said process acting both as a reactant as well as a catalyst for the reaction.

8. The process which comprises heating dimethallyl amine and hydrogen sulfide and removing from the product so formed the fraction thereof volatilizing below about 100 C. at 5 cin. mercury pressure, the diallyl amine in said process acting both as a reactant as well as a catalyst for the reaction.

9. The process which comprises heating a dialkenyl ether and hydrogen sulde in the presence of from 1 to 10 mol per cent of an aliphatic amine and removing from the product so formed the fraction thereof volatilizing below 100 C, at 5 cm. mercury pressure.

10. The process which comprises heating a dialkenyl ether and hydrogen sulfide in the presence of from 1 to 10 mol per cent of a basic catalyst and removing from the product so formed the fraction thereof volatilizing below 100 C. at 5 cm. mercury pressure.

11. The process which comprises heating a dialkenyl ether and an aliphatic dimercaptan in the presence of from 1 to 10 mol per cent of an aliphatic amine and removing from the product so formed the fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure.

12. The process which comprises heating a dialkenyl ether and an aliphatic dimercaptan in thepresence of from 1 to 10 mol per cent of a basic catalyst and removing from the product so formed the fraction thereof volatilizing below about C. at 5 cm. mercury pressure.

13. The process which comprises heating a compound having the formula RXR with a compound selected from the group consisting of hydrogen sulfide and the aliphatic dimercaptans in the presence of from 1 to 10 mol per cent of an aliphatic amine and removing from the product so formed a fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure, the Rs in said formula representing alkenyl radicals and the X representing a member selected from the group consisting of -O-, S, and

RL lt wherein R1 is selected from the group consisting of the hydrogen atom and the monovalent organic radicals.

14. The process which comprises heating a compound having the formula R-X-R with a compound selected. from the group consisting of r hydrogen sulde and the alphatic dimercaptans in the presence of from l to 10 mol per cent of a basic catalyst and removing from the product so formed a fraction thereof volatilizing below about 100 C. at 5 cm. mercury pressure, the Rs in said formula representing alkenyl radicals and the X representing a member selected from the group consisting of -O, -S-, and

lli N- wherein R1 is selected from the group consisting of the hydrogen atom and the monovalent organic radicals.

WILLIAM E VAUGHAN.

DENHAM HARMAN.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,517,564 Harman et al Aug. S, 1950 2,562,844 Harman et al July 31, 1951 OTHER REFERENCES Gabriel et al., Ber. Deut. Chem., vol. 30, page 2497 (1897). 

13. THE PROCESS WHICH COMPRISES HEATING A COMPOUND HAVING THE FORMULA R-X-R WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF HYDROGEN SULFIDE AND THE ALIPHATIC DIMERCAPTANS IN THE PRESENCE OF FROM 1 TO 10 MOL PER CENT OF AN ALIPHATIC AMINE AND REMOVING FROM THE PRODUCT SO FORMED A FRACTION THEREOF VOLATILIZING BELOW ABOUT 100* C. AT 5 CM. MERCURY PRESSURE, THE R''S IN SAID FORMULA REPRESENTING ALKENYL RADICALS AND THE X REPRESENTING A MEMBER SELECTED FROM THE GROUP CONSISTING OF -O-, -S-, AND 